CONTRAT 119 MECANIQUE PROCESS

SECTION CLINKER ET BROYAGE CIMENT

ANNEXE 5

cover page mode/-annex5.docm 10 avril 2007

 Research and Development

Laboratory Report

Raw Material Investigation for the Production of Portland

Cernent Clinker

1 I

Beckum, 13.10.2006

Code word: Customer:

Ciments du Sahel
Senegal

Material no.: Job no.:

WE 11480 23 07 2573

S:\Dept\A300a11\340\Projekte\Projekte2006\Ciments du Sahel - W E 11480\Ber11480.doc

Polysius AG Chairman of Supewisory Board:

Graf-Galen-StraBe 17,
D-59269 Beckum-Neubeckum.Germany
Phone: +49-(0)2525-99-0
Telefax: +49-(0)2525-99-2100,Telex: 89481-0 PBK D
E-Mail: polysius@thyssenl<rupp.com
Internet: www.polysius.com
Dr. Hans Christoph Atzpodien
Executive Board: Jürgen Bauer, Chairman
Dr. Friedrich-Wilhelm Dierkes, Dipl.-lng. Lothar Jungemann,
Dr.-lng. Detlev Kupper, Dr.-lng. Detlev Rose
Trade Register: Amtsgericht Munster HRB-Nr. 7717
Certified to ISO 9001 Registered Office: Beckum-Neubeckum

3
We reserve al1 rights in connection with this documentation also in case that a patent or
utility model is registered. Without Our previous written consent this documentation may
neither be copied nor made available to third parties nor be used in other unauthorized
manner.

All recommendations and results exclusively refer to the samples analysed by us.

Writer: Department:
Fabian 340
Report no.: Location of original report:
241 340
Signatures:

-
S:\Dept\A300a11\340\Projekte\ProjektePOOô\Ciments du Sahel WE 11480\Berl1480.doc

Polysius AG Chairrnan of Supe~isoryBoard:

Graf-Galen-StraBe 17,
D-59269 Beckum-Neubeckum, Gerrnany
Phone: +49-(0)2525-99-0
Telefax: +49-(0)2525-99-2100, Telex: 89481-0 PBK D
E-Mail: polysiusQthyssenkrupp.com
Internet: www.polysius.com
Dr. Hans Christoph Atzpodien
Executive Board: Jùrgen Bauer, Chairman
Dr. Friedrich-Wilhelm Dierkes, Dipl.-lng. Lothar Jungemann,
Dr.-lng. Detlev Kupper, Dr.-lng. Detlev Rose
Trade Register: Arntsgericht Munster HRB-Nr. 7717
Certified to ISO 9001 Registered Office: Beckum-Neubeckurn

7*
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Table of contents

1 Preliminary remarks and object of tests .............................................................................

14

2 List of material ...................................................................................................................

4

3 Summary and findings .......................................................................................................

5

4 Raw material testing .................................................................................................... 111

4.1 General assessment of raw material on arriva1........................................................./ 11

5 Chemical analysis of raw materials............................................................ . . .........115

5.1 Methods of analysis ..................................................................................................
115

6 Fuel data ....................................................................................................................... 117

7 Raw meal synthesis for empirical tests ............................................................................

119
7.1 Raw meal synthesis ..................................................................................................
/ 19
7.2 Determination of raw mixture burnability...............................................................122
7.3 Calculation of separation factors - nature of precipitator dust..................................125

8 Calculation formulas used ........................................................................................ 2 7

annex
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4

1 Preliminary remarks and object of tests

The materials under investigation were analysed with respect to their chemical composition.
A raw mixture suitable for the production of Portland Cement was prepared using the sam-
ples provided by the client and its burnability tested according to the standard POLYSIUS
burnability test.

2 List of material

The materials provided by the client for investigation are summarised in table 1 together
with the respective date of arrival in the POLYSIUS Research Centre, sample quantity and
laboratory identification. Material designations are used as provided by the client throughout
the whole report. For any further inquiries refer to the given laboratory investigation number.

Laboratory identification: WE 11480

Date of arrival: 04.09.2006

Table 1: Designation of materials

Designation Quantity [kg]

l
Melange Crue 91O
Calcaire HT 210
Laterite 160
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3 Summary and findings

- Melange Crue

Melange Crue is a mixture of limestone ( Calcaire ) and an argillaceous component.

The concentrations of detrimental elements are al1 in the lower range except of phospho-
rous which reveals a higher value.

The moisture content after the under water storage procedure is high due to the high porti-
on of fine material ( about 35 % < 1 mm ). After storage under water the mixture becomes
sticky and slightly smeary. Handling problems during transport and storage of the moist
material therefore are very likely.

Photo 1: Melange Crue on arrival; the mixture contains a high portion of fines
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- Calcaire HT

Calcaire HT lies in the upper range of marly limestones from the chemical point of view.
The concentrations of the alkalis and chlorine are low while SOSshows an average value.
The amount of P205 is high compared with other limestones.

The moisture content on arrival reveals an average value. After storage under water the
moisture content increases distincly to a high value compared with other limestones. The
reason for this is the high portion of fine material ( about 45 % .:1 mm ) which tends to be
sticky and slightly smeary if rnoistened.
Therefore, handling problems have to be expected if the material becomes wet.

Photo 2: Calcaire HT on arrival; the material contains a high portion of fines

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The chemical composition of Laterite lies in the wide range of typical laterites. Laterite is a
low grade iron component with a correspondingly higher amount of Sion and lower amount
of A1203.
The amounts of alkalis and chlorine are low while sulfur and phosphorous show increased
values.
The amount of Fen03in Laterite is this low so that the designation ,,SonstigesUhas to be
allocated according to the POLYSIUS interna1 classification of raw materials.

Laterite is mainly non-magnetic; only very few of the fines are magnetic.

The moisture content on arrival is low but after storage under water the moisture content
increases to a comparably avarage value. Nevertheless, the fine portion of Laterite tends
to be sticky and slightly smeary. For this reason, handling problems with the moist material
have to be expected.

Photo 3: Laterite on arrival

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- Mixture No. 2

The raw mixture was calculated with the modules being in the range of the values given in
the tender document ( LSF = 93.8 ; SR = 2.45 ; AR = 1.48 ). Since Mixture No. 2 is a 3-
component mixture only, the value for the alumina ratio cannot be fixed.

The raw mixture contains 0.05 % C and c 0.01 % s2-( calculated from the raw materials ).

As combustible, the data of a South African Coal were used. The heat consumption was set
to be 730 kcallkg clinker.

In case that petcoke would be used as an additional combustible, it would be very probable
that coatings rich in sulfur would occur in the kiln inlet zone. Their removal should be fore-
seen !
It is further recommended to increase the amount of petcoke in the combustible mix step by
step and to observe the respective influence on the burning process.

- Burnability test

At a lime standard of 95.0, the investigated Mixture No. 2 is classified to be in the range of
very easy burnabililty (B195.0= 47).

- Separation factors
The separation factors SFK= 0.87 and SFs = 1.O2 lie within the acceptable range of 0.8 -
1.2. Therefore, a separate handling of filter dust is not necessary from the chemical point of
view.
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Table 2: Summaw of test results

Mixture No. 2
% Melange Crue 67.49
% Calcaire HT
% Laterite
Silica ratio
Alumina ratio
Lime standard (acc. to KUEHL)
SiO2/(AI2O3+ Ti02) 4.02
Potential phase composition
% C3S )
% CnS )
% CA
, ) acc. to BOGUE

% Liquid phase acc. to LEA (1400 C) 25.2

Empirical Laboratory Investigation
1 Fineness R [%] 200 pm 1 1.2
Fineness R [%] 90 pm
Burnability test BI
BI-Value
Lime standard of: 90.0
1 Lime standard of: 93.3
1 Lime standard of: 95.0
Lime standard of: 100.0 92
lntake of lmpurities
Raw Mix (free of LOI)

Separation factor SF ( lime standard ) 0.87

Separation factor SF ( silica ratio ) 1.O2
% Na2O+ 0.658 % K20 0.25
Fuel % S ( anhvdrous ) 0.54
% S03 = 730 kcallkg clinker 0.16
total S03 % (in clinker) 0.38
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PolYS ius
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4 Raw material testing

4.1 General assessment of raw material on arrival

This test embraces the general description of the raw material and the determination of the
material's characteristics on arrival.

In addition, some characteristic material properties are determined which are essential for
instance for the design of raw material conveying and raw material storage facilities. The
general assessment of the materials is listed in table 3 and their particle-size distribution is
listed in table 4.

The "General raw material assessment" includes the determination of the moisture content.
The moisture values of the material "on arrival" may not, however, be completely represen-
tative for the material in the quarry, which is subject to local influences (quarrying method,
weather and type of raw material storage), as the samples might have dried out due to long
transportation andlor storage.

In periods of high precipitation it can be expected that the moisture content in the heap of
material blasted from the quarry face andlor the material lying in nonroofed storage areas
will approach the figure indicated by the "underwater storage values". For this test, crushed
feed of O - 30 mm has been used.

Bulk density (kg/l) of feed

"1
Use this value as a basis for calculating the capacity of conveying units (belts deep bucket
conveyors, bucket elevators etc.).

Bulk density (kg/l) after shaking

Use this value as a basis for calculating the capacity of storage facilities with known filling
volumes (silos, blending beds etc.).
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Table 3: General assessment of raw materials, outward appearance, moisture content and
under water storage results
Material Melange Crue
I.D. code for bulk material Sonstiges
Bulk density of feed [kgll]
a) moist 1.45 ( as delivered )
b) dried 1.61 ( as delivered )
Bulk density after shaking [kgll]
a) moist 1.62 ( as delivered )
b) dried 1.76 ( as delivered )
Moisture [%]
on receipt 4.4
after 3-days storage 22.7
under water
behaviour during sticky and smeary due to
under water storage the high portion of fines
Colour* very pale orange 1OYR 812
to grayish orange1OYR714
Structure, fabric mixture of limestone and
an argillaceous component;
the argillaceous component
cannot be identified becau-
se it is incorporated in the
fines
Strength, fracture coarse particles are relati-
vely soft with angular frac-
tu re
Calcaire HT
K
1.43 ( as delivered )
1.64 ( as delivered )
1.56 ( as delivered )
1.80 ( as delivered )
2.2
15.4
sticky and slightly smeary
due to the material's fine-
ness
very pale orange 10YR 812
fine- to medium-crystalline,
homogeneous, with rec-
rystallized biogenetic relics,
abundant fines
coarse particles are relati-
vely soft, angular fracture

* Colours according to "Rock Color Chart" of the American Geological Soc.

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Table 3 continued
Materiai Laterite
I.D. code for bulk material Sonstiges
Bulk density of feed [kgll]
a) moist
b) dried 1.66 ( after jaw crusher )
Bulk density after shaking [kgll]
a) moist
b) dried 1.77 ( after jaw crusher )
Moisture [%]
on receipt 2.7
after 3-days storage 16.5
under water
behaviour during sticky and slightly smeary due
under water storage to the fine portion
Colour* light brown 5YR 516
Structure, fabric inhomogeneous concretions
and agglomerates of quartz-
grains and various Fe-oxides /
hydroxides, fine- to medium-
grained; mainly non-magnetic,
only few of the very fine
particles are magentic
Strength, fracture relatively soft, uneven fracture

Lump size on delivery [mm]

about 10% 100 - 120 mm
about 20% 20 - 100 mm
about 40% 5-20mm
about 30% c5mm

* Colours according to "Rock Color Chart" of the American Geological Soc.

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Table 4: Particle size distribution of raw materials

Material
1 = Melange Crue as delivered
2 = Calcaire HT as delivered
3 = Laterite see general assessrnent of raw materials
Particle Size [mm] 1 [%] 2 [%]
31.5 1.O
22.4
16.0
11.2
8.0
5.6
4.0
2.8
2.0
1.4
1.O
0.71O
0.500
0.355
0.250
0.200
0.160
0.125
0.090
0.063
0.045
0.032
< 0.032
Total
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5 Chernical analysis of raw materials

5.1 Methods of analysis

The main oxides were determined by fused bead X-ray fluorescence (XRF). Sodium (Na as
Na20) and potassium (K as K20) were determined using Atom Absorption Spectroscopy
(AAS). Chlorine (CI) was determined wet-chemically with the titration method according to
VOLHARD. The total sulphur (S as SOS)was determined by automatic infrared analyser
( LEC0 CS-200 ). The loss on ignition (LOI) refers to the percentage loss (or gain) of sam-
ple mass after 30 minutes residence time at 1050 C .

All raw materials were analysed by POLYSIUS and the following tests were carried out
either using the available raw materials or using the respective chemical analyses.
The results of the chemical analyses are shown in table 5.
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Table 5: Results of chemical raw material analyses carried out by POLYSIUS

Material
1 = Melange Crue
2 = Calcaire HT
3 = Laterite
1 2 3
% LOI 34.16 42.21 8.69
% SiOa 17.59 2.81 45.88
% 3.80 0.68 9.78
% Ti02 0.27 0.04 0.73
% Fe203 1.74 0.29 34.28
% Mn203 0.02 0.01 0.01
% Ca0 41.05 53.04 0.10
% Mg0 0.43 0.35 0.03
% S03 ( total sulfur ) 0.15 0.10 0.35
% P205 0.38 0.30 0.74
OO
/ Na20 0.03 0.01 0.02
% K20 0.28 0.03 0.14
% CI 0.006 0.001 0.001
% Total 99.91 99.87 100.75
% s2- < 0.01 < 0.01 < 0.01
Silica ratio 3.02 2.75 1.O2
Alumina ratio 2.31 2.40 0.31
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6 Fuel data

A South African coal should be applied as combustible. Since the respective coal was not
delivered as a sample, al1 calculations were based on the coal data given in the tender
document
( table 6 ).
In order to carry out the burnability test, an ash was taken from Our raw material stock ha-
ving a similar chemical composition as the ash quoted in the tender document ( se table 7
1.

Table 6: Fuel data from tender

Material: South African Goal ( client data )
Proximate-Analysis air dry anhydrous
% Moisture (Karl-Fischer )
% Volatile matter
% Ash 14.0
% Fixed carbon (diff. to 100)
% Total
Ultimate Analysis
% Ash
%C
%H
%S 0.54
% CI
%N
% O (diff. to 100)
% Total
Gross calorific value (Ho)
kJ1kg
kcallkg
Net calorific value (Hu)
kJ1kg
kcallkg 6200
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Table 7 : Ash analysis of coal and influence of ash on raw meal

47.82 ( 49.98)
31.04 (38.16)

% Pz05 2.10 (0.31) 0.04

% NanO 0.15 ( 0.04) 0.00
% K20 0.54 ( 0.36) 0.07
% CI
Total ( 103.22 ) 1.84
Silica ratio 1.30
Alumina ratio 8.46
Fuel consumption g coal 1 100.00 g clinker 11.78
Ash influence g ash 1 100.00 g coal 14.60
g ash 1 11.78 g coal 1.72
g ash 1 100.00 g raw meal 1.10

* total intake of fuel, calculated from the elementary analysis

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7 Raw meal synthesis for empirical tests

For preparing a raw meal sample the primarily crushed (c2 mm) raw materials are ground
to a fineness of 1.2 to 1.5 % > 200 pm in a vibratory disc mill. After separation of this frac-
tion the residual mixture quantity is adjusted to a fineness of 12 to 15 % > 90 pm. After-
wards, the material which had been separated before, is again mixed intensively with the
mixture. The raw meal mixture made in this way is suitable for the determination of separa-
tion tendencies and for the determination of the burnability index ( BI ), ash is added ac-
cording to the calculated portion.

7.1 Raw meal synthesis

The proportioning of the raw materials in the mixture under investigation was calculated with
the modules being in the range of the values given in the tender document.

The investigated mixture contains 0.05 % C and c 0.01 % s2-( calculated from raw material
analyses ).

Since no coal sample was available, client's data about a coal were used to calculate the
raw mixture. For the preparation of the raw meal of Mixture No. 2, a coal ash was used from
Our raw material stock which has similar chemical composition as client's data.

The heat consumption was set to be 730 kcallkg clinker.

When using a coal from South Africa ( as in Mixture No. 2 ) then the molar ratio between
the alkalis and sulfur is balanced ( degree of sulphatization SG = 117 ).

In case that petcoke will be used as combustible with a correspondingly high sulfur content,
then the a.m. molar ratio will change in favour to the sulfur ( SG >> 100 ), thus meaning that
coatings rich in sulfur would occur in the kiln inlet zone. Appropriate measures for their
removal would have to be foreseen.
Additionally it is recommended to only gradually increase the amount of petcoke in a com-
bustible mix step by step and to monitor the resulting effects.
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Table 8: Mixing calculation

heat consumption:

% S03 (total sulfur)

% P205 0.37 0.57 0.61 0.60
% Na2O 0.02 0.04 0.04 0.04
% K20 0.20 0.31 0.32 0.32
% CI O. 004 0.007 0.009 0.009
Total 99.92 100.00 101.84 100.00
% Na2Oequivalent 0.25
%C O. 05
% s2- < 0.01
Silica ratio 2.53 2.45
Alumina ratio 1.43 1.57
Lime standard (KUEHL) 97.6 93.8
Clinker phases (Bogue)
% C3S 59.2
o/, C2S 19.3
% C3A 8.7
o/, C4AF 10.8
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7.2 Determination of raw mixture burnability

A burnability test was carried out with Mixture No. 2 according to the standard POLYSIUS
burnability test.

For the burnability test the laboratory raw meal is prepared as follows:

First, the raw mixture is moistened with water in a porcelain basin until plastic consistency is
reached. Then the sample is divided into equal portions and 20 equally sized granules
(1.5 cm3 = 1.4 cm diameter) are manually formed.

These granules are dried for 120 minutes at 105%.

In an electrically heated laboratory muffle furnace the granules are preheated for 30 min-
utes at 600C in a platinum dish. The granules then are burnt at temperatures of 1350%,
1400C, 1450C and 1500C in a muffle furnace. The residence time at the respective
temperatures is 15 minutes.

The granules of each temperature range are ground in a laboratory vibrating miIl until the
analysing fineness is reached and the content of free lime is determined chemically accord-
ing to FRANKE.

The burnability index evaluated from the values for free lime is calculated with a method
which is based on extensive tests with numerous raw meal samples. Tests with more than
520 different raw meals of 68 countries form the reference. The mean value of al1 the Sam-
ples corresponds to a BI9, of 100.

The BI-value determined for the respective sample can be assigned to one of seven burn-
ability classes.

very easy burnability

easy burnability
normal burnability
slightly difficult burnability
--
I
difficult burnabilitv
140 - 160 1 very difficult burnability
Polysius

1> 160 1 extremely difficult burnability 1 --

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The results of the burnability test are summarised in table 9. Mixture No. 2 is in the range of
very easy burnability, showing a B193.3of 37 compared to the average value of 100.
The respective burnability at a lime standard of 95.0 would be BIg5.~ = 47
( very easy burnability as well).

The attached diagram (annex) allows to extrapolate the respective burnability index for a
different lime standard. The control analysis allows to check the performed mixing calcula-
tion and the preparation of the test raw mixture.

'1
'"
Table 9: Results of the burnability test
Mixture No. 2
Burnability test Raw mix controi analysis
Raw meal fineness: R [%]
200 pm 1.2
90 pm 13.8
Burning temperature Ca0 ( acc. to Franke )
[Cl [Y01
1350 4.05

BI at a lime standard = 90
BI at a lime standard = 93.3
BI at a lime standard = 95 Lime standard (Kuehl)

normal burnability
100 - 120 slightly difficult burnability
120 - 140 difficult burnability
 .,
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9

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Polysius
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7.3 Calculation of separation factors - nature of precipitator dust

General remarks

The separation factor is determined as the ratio between the chemical composition of the
fraction c 32 Pm and the overall raw meal analysis. Experience has shown that precipitator
dusts - apart from subsequent agglomerations - generally lie within the very fine particle
size range. Detailed tests have further shown that the chemical analysis of kiln-feed mate-
rial particles in the size range O - 32 Pm in most cases correspond very well or at least tend
to agree to a high percentage with the chemical composition of the precipitator dust
(approx. 95 % certainty). Therefore the chemical analysis of the size fraction O - 32 Fm of a
model raw meal can supply information about the probable chemical composition of the
precipitator dust to be expected in pure kiln operation. The normal range of separation (or
segregation) factors found for typical raw mixtures lies between 0.8 - 1.2. Using this factor,
it can be shown to what extent changes in raw meal composition might occur as a result of
segregation, or whether a dust concentration of extreme chemical composition can be
expected during the later production stages.
The results of this investigation are given in table 10.
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Table 10: Comparison of expected filter dust (fraction O - 32 vm) and raw meal

2.21 3.38 2.26 3.52

% Mn203 0.03 0.04 0.02 0.03
% Ca0 42.24 64.57 43.41 67.70

Silica ratio 2.57 2.53

Alumina ratio 1.73 1.43
Lime standard (KUEHL) 84.8 97.6
SFK 0.87
SFs 1.O2

The separation factors SFK= 0.87 and SFs = 1.02 lie within the acceptable range of 0.8 -
1.2. Therefore, a separate handling of filter dust is not necessary from the chemical point of
view.
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8 Calculation formulas used

Silica ratio =

% Alz 0 3
Alumina ratio =
% Fe2 0 3

100 * % C a 0
Limestandard acc. to KUEHL =
2,8 * % SiO2 + 1,1 * % A1203 + 0,7 * % Fez03

Silicic acid module acc. to MUSSGNUG =

Liquid phase acc. to LEA (bei 1.400 C)

2.95 * % AI2O3+ 2.2 * % Fen03+ % Mg0 (max. 2 %) + % Na20+ % K20

Annotation: For separate determination of Ti02 und Mn203,Ti02 is included in

AI2O3and Mn203in Fe203when calculating the ratios
i
7N-k